Effect of ionomer content and relative humidity on polymer electrolyte membrane fuel cell (PEMFC) performance of membrane-electrode assemblies (MEAs) prepared by decal transfer method

Membrane-electrode assemblies (MEAs) were fabricated by the decal transfer method with various Nafion ionomer contents (10–40 wt%) and their single cell performance and electrochemical characteristics were examined in atmospheric air at relative humidities of 25–95%. At high humidity (95%), the MEA performance was the highest with a cathode ionomer content of 30 and 20 wt% at 0.6 and 0.4 V, respectively. The optimum ionomer content of the decal MEAs increased with decreasing humidity, because of the change in the oxygen transport rate (water flooding) and number of active sites (ionic resistance). The concentration overpotential gradually increased with relative humidity up to about 0.4 V at 0.8 A/cm², which was not considered in previous studies using pressurized air and oxygen. The combined effect of the electrochemical active surface area and ionic resistance of the cathodes on the activation overpotential was also investigated, focusing on intermediate and low humidity levels, using a newly developed impedance analysis method.     

The effects of relative humidity on the performances of PEMFC MEAs with various Nafion ionomer contents

For PEMFC operation, water management is very important to provide both sufficient proton conductivity and mass transport. Therefore, in this study, the effect of the relative humidity (38–87%) on cell performance is examined for PEMFC MEAs with various Nafion^® ionomer contents. The MEAs were fabricated using a CCM (catalyst-coated membrane) spraying method. As the relative humidity of the cathodes (RHC) increases, the cell voltages at 0.4 and 1.2 A/cm² increased for a MEA with 20 wt% ionomer. This can be explained in terms of the expansion of active sites with enhanced ionic conductivity (activation overpotential). In contrast, with a higher RHC value, the cell voltages for 35 wt% ionomer (more hydrophilic) gradually decreased as a result of slower gas transport (concentration overpotential). For MEAs with intermediate ionomer contents, 25 and 30 wt%, the cell voltages at 0.4 A/cm² showed maximum values at a RHC of 67%, at which point the mass transport begins to be the more dominant factor. The highest unit cell performance was observed in a MEA with an ionomer content of 25 wt% at a RHC of 59% and in a MEA at 20 wt% ionomer content at a higher humidity of 87%.     

A comparative study of CCM and hot-pressed MEAs for PEM fuel cells

A comparative investigation was performed on PEM fuel cells made with conventional hot-pressed MEAs and catalyst-coated membranes (CCM) under identical conditions of Pt electrolcatalyst loadings. The results showed that cells with a CCM exhibit significantly higher electrochemical performance and power density than those prepared with conventional hot-pressed MEAs. Cyclic voltammetric and impedance studies showed that the MEAs prepared by the CCM method have a higher electrochemical surface area, low cell ohmic resistance and low charge transfer resistance as compared to those prepared with hot-pressed MEAs and the same Pt loading. The results demonstrate that a CCM can enhance the utilization efficiency and improve the catalyst layer and membrane interface of PEM fuel cells.     

Low temperature decal transfer method for hydrocarbon membrane based membrane electrode assemblies in polymer electrolyte membrane fuel cells

Decal transfer is an effective membrane electrode assembly (MEA) fabrication method known for its low interfacial resistance and suitability for mass processing. Previously decal transfer for hydrocarbon membranes was performed at temperatures above 200 °C. Here a novel low temperature decal transfer (LTD) method for hydrocarbon membranes is introduced. The new method applies a small amount (2.2 mg cm⁻²) of liquid (1-pentanol) onto the membrane separator before decal transfer to lower the T_g of the membrane and achieves complete decal transfer at 110 °C and 6 MPa. Nafion binder amount in the catalyst layer and catalyst layer annealing temperature is controlled to optimize the fuel cell performance. Compared to conventional decal transfer (CDT), the novel LTD method shows enhancement in energy efficiency, simplicity in the process scheme, and improvement in fuel cell performance.     

Hydrocarbon-based electrode ionomer for proton exchange membrane fuel cells

The electrode ionomer is a key factor that significantly affects the catalyst layer morphology and fuel cell performance. Herein, sulfonated poly(arylene ether sulfone)-based electrode ionomers with polymers of various molecular weights and alcohol/water mixtures were prepared, and those comprising the alcohol/water mixture showed a higher performance than the ones prepared using higher boiling solvents, such as dimethylacetamide; this is owing to the formation of the uniformly dispersed ionomer catalyst layer. The relation between ionomer molecular weight for the same polymer structure and the sulfonation degree was investigated. Because the chain length of polymer varies with molecular weight and chain entanglement degree, its molecular weight affects the electrode morphology. As the ionomer covered the catalyst, the agglomerates formed were of different morphologies according to their molecular weight, which could be deduced indirectly through dynamic light scattering and scanning electron microscopy. Additionally, the fuel cell performance was confirmed in the current-voltage curve.     

The effects of ionomer content on PEM water electrolyser membrane electrode assembly performance

In this study, the effects of Nafion^® ionomer content in membrane electrode assemblies (MEAs) of polymer electrolyte membrane (PEM) water electrolyser were discussed. The MEAs were prepared with a catalyst coated membrane (CCM) method. The catalysts inks with Nafion ionomer could form uniform coatings deposited on the membrane surfaces. SEM and area EDX mapping demonstrated that anode catalyst coating was uniformly distributed, with a microporous structure. The contents of Nafion ionomer were optimized to 25% for the anode and 20% for cathode. A current density of 1 A cm⁻² was achieved at terminal voltage 1.586 V at 80 °C in a PEMWE single cell, with Nafion 117, Pt/C as cathode, and Ru_0.7Ir_0.3O₂ as anode.     

Development of shut-down process for a proton exchange membrane fuel cell

Several different shut-down procedures were carried out to reduce the degradation of membrane electrode assembly (MEA) in a proton exchange membrane fuel cell (PEMFC). The effects of close/open state of outlets of a single cell and application of a dummy load during the shut-down on the degradation of the MEA were investigated. Also, we elucidated the relationship between the thickness of the electrolyte membrane and the degradation of the MEA for different shut-down procedures. When a thin electrolyte membrane was used, the closer of outlets mitigated the degradation during on/off operation. For the thicker electrolyte membrane, the dummy load which eliminates residual hydrogen and oxygen in the electrodes should be applied to lower the degradation.     

Optimisation of carbon nanofiber based electrodes for polymer electrolyte membrane fuel cells prepared by a sedimentation method

Tubular carbon nanofibers with an average diameter of 150 nm are investigated as a possible material for the electrodes preparation for polymer electrolyte membrane fuel cells. Well-dispersed platinum particles with an average crystallite size of 4.6 nm are deposited on surface-oxidised fibers to be used as a catalyst support with an electroless plating method. The carbon nanofiber-based electrodes are prepared by a sedimentation method without the use of organic solvents. This method allows an exact setting of the fiber and binder content and the catalyst loading. The electrodes are optimised by varying the thickness of the gas diffusion layer and its binder content as well as the thickness of the active layer. These optimised electrodes show a considerably better performance when compared to carbon black-based electrodes with the same catalyst loading prepared by a spraying process using the same type and amount of electrolyte in the membrane electrode assembly. By reducing the platinum content from 0.7 to 0.2 mg cm⁻², catalyst utilisation is significantly increased.     

Prediction of the effective conductivity of Nafion in the catalyst layer of a proton exchange membrane fuel cell

In a previous study, a simple acid catalyzed reaction (esterification) was found to predict excellently conductivity of a membrane contaminated with NH₄⁺ or Na⁺. Since measurement of the conductivity of Nafion in a catalyst layer is problematic, being able to predict this conductivity for various formulations and fuel cell conditions would be advantageous. In this study, the same methodology as before was used to examine the proton availabilities of supported Nafion (Nafion on carbon and on Pt/C), as exists in the catalyst layer used in a PEMFC, during impurity exposure (e.g., NH₃) as a means for prediction of its conductivity. It was found that the effect of NH₃ exposure on the proton composition (yH+) of supported Nafion was similar to that of N-211 under the same conditions. Determined values of yH+ were then used to estimate the effective conductivity of an ammonium-poisoned cathode layer using the correlation developed and the agglomerate model. The predicted conductivities were matched with the results available in the literature. This technique would be useful for the optimization of catalyst design and for fuel cell simulation, since it provides many benefits over conventional performance test procedures.     

Amelioration of PEMFC performance at high temperature by incorporation of nanofiller (sepiolite/layered double hydroxide) in Nafion membrane

Nanoheterostructured material composed of sepiolite clay mineral in which is assembled a MgAl layered double hydroxide (LDH) was used in the preparation of Nafion composite electrolyte membranes and their behavior compared to those of membranes filled with the LDH alone. Both, the neat MgAl LDH and the MgAl LDH-sepiolite hybrid materials were obtained via the co-precipitation method. Sepiolite fibers provide a large external surface area for bonding MgAl LDH particles while maintaining high microporosity and water molecules. The nanocomposite membranes were prepared incorporating different amount of LDH or LDH-sepiolite hybrid. Composite membranes present better water retention, good thermal properties and high proton conductivities at high temperatures than the pure Nafion membrane. The proton conductivity at 100 °C and 100% RH reaches a value of 0.13 S/cm for the LDH-sepiolite Nafion membrane whereas is only 0.010 S/cm in the case of the Nafion membrane. Fuel cell tests using Nafion membranes containing LDH or LDH-sepiolite hybrid as composite electrolytes show a good result for the operation of the PEMFC at 80 °C, 100 °C and 110 °C, with a clear favoring effect of the LDH-sepiolite filler for operation at the highest temperatures.     

Performance of an ultra-low platinum loading membrane electrode assembly prepared by a novel catalyst-sprayed membrane technique

Membrane electrode assemblies (MEAs) with ultra-low platinum loadings are attracting significant attention as one method of reducing the quantity of precious metal in polymer electrolyte membrane fuel cells (PEMFCs) and thereby decreasing their cost, one of the key obstacles to the commercialization of PEMFCs. In the present work, high-performance MEAs with ultra-low platinum loadings are developed using a novel catalyst-sprayed membrane technique. The platinum loadings of the anode and cathode are lowered to 0.04 and 0.12 mg cm⁻², respectively, but still yield a high performance of 0.7 A cm⁻² at 0.7 V. The influence of Nafion content, cell temperature, and back pressures of the reactant gases are investigated. The optimal Nafion content in the catalyst layer is ca. 25 wt.%. This is significantly lower than for low platinum loading MEAs prepared by other methods, indicating ample interfacial contact between the catalyst layer and membrane in our prepared MEAs. Scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) measurements reveal that our prepared MEA has very thin anode and cathode catalyst layers that come in close contact with the membrane, resulting in a MEA with low resistance and reduced mass transport limitations.     

Manufacturing catalyst-coated membranes by ultrasonic spray deposition for PEMFC: Identification of key parameters and their impact on PEMFC performance

This study deals with the manufacturing of catalyst-coated membranes (CCMs) for newcomers in the field of coating. Although there are many studies on electrode ink composition for improving the performance of proton-exchange membrane fuel cells (PEMFCs), there are few papers dealing with electrode coating itself. Usually, it is a know-how that often remains secret and constitutes the added value of scientific teams or the business of industrialists. In this paper, we identify and clarify the role of key parameters to improve coating quality and also to correlate coating quality with fuel cell performance via polarization curves and electrochemical active surface area measurements. We found that the coating configurations can affect the performance of lab-made CCMs in PEMFCs. After the repeatability of the performance obtained by our coating method has been proved, we show that: (i) edge effects, due to mask shadowing - cannot be neglected when the active surface area is low, (ii) a heterogeneous thickness electrode produces performance lower than a homogeneous thickness electrode, and (iii) the origin and storage of platinum on carbon powders are a very important source of variability in the obtained results.     

Effects of sulfonated polyether-etherketone (SPEEK) and composite membranes on the proton exchange membrane fuel cell (PEMFC) performance

Sulfonated polyether-etherketone (SPEEK) has a potential for proton exchange fuel cell applications. However, its conductivity and thermohydrolytic stability should be improved. In this study the proton conductivity was improved by addition of an aluminosilicate, zeolite beta. Moreover, thermohydrolytic stability was improved by blending poly-ether-sulfone (PES). Sulfonated polymers were characterized by H-NMR. Composite membranes prepared were characterized by Electrochemical Impedance Spectroscopy (EIS) for their proton conductivity. Degree of sulfonation (DS) values calculated from H-NMR results, and both proton conductivity and thermohydrolytic stability was found to strongly depend on DS. Therefore, DS values were controlled time in the range of 55–75% by controlling the reaction time. Zeolite beta fillers at different SiO₂/Al₂O₃ ratios (20, 30, 40, 50) were synthesized and characterized by XRD, EDX, TGA, and SEM. The proton conductivity of plain SPEEK membrane (DS = 68%) was 0.06 S/cm at 60 °C and the conductivity of the composite membrane containing of zeolite beta filled SPEEK was found to increase to 0.13 S/cm. Among the zeolite Beta/SPEEK composite membranes the best conductivity results were achieved with zeolite beta having a SiO₂/Al₂O₃ ratio of 50 at 10 wt% loading.     

Effects of platinum loading on the performance of proton exchange membrane fuel cells with high ionomer content in catalyst layers

The effect of Pt loading on the performance of proton exchange membrane fuel cells with atmospheric air feed was evaluated at various relative humidities. The membrane electrode assemblies (MEAs) were fabricated by decal methods with high Nafion ionomer content (30 and 40 wt.%). When the Pt loading was decreased, the performance of the MEAs with an ionomer content of 30 wt.% gradually decreased, mainly due to the insufficient active Pt surfaces with low proton conductivity. With a higher ionomer content of 40 wt.%, the activation overpotential was not significantly increased by the decrease in Pt loading, and the concentration overpotential could be largely reduced by decreasing the Pt loading to 0.25 mg/cm². When the Pt loading was further decreased to 0.15 mg/cm², even though the flooding became more severe, the cell performance at 0.6 V and intermediate relative humidity of 55% was about 71.6%, compared to the MEA with a high Pt loading of 0.35 mg/cm² (ionomer content: 30 wt.%). The cell performance could be further enhanced by decreasing the ionomer content in the anode to enhance the water back diffusion.     

A study on fabrication of sulfonated poly(ether ether ketone)-based membrane-electrode assemblies for polymer electrolyte membrane fuel cells

The porosity effect of catalyst electrodes in membrane-electrode assemblies (MEAs) using a hydrocarbon-based polymer as electrolyte and ionomer was investigated on physical and electrochemical properties by varying the content of ionomer binder (dry condition) in the catalyst electrodes. The MEAs were compared with the Nafion^®-based MEA using Nafion^® 112 and 5 wt.% ionomer solution (EW = 1100) in terms of porosity values, scanning electron microscopic images, Nyquist plots, dielectric spectra and I–V polarization curves. In this study, sulfonated poly(ether ether ketone) (SPEEK) membranes with 25 ± 5 μm of thickness and 5 wt.% ionomer solutions have been prepared. The prepared membranes were characterized in terms of FT-IR, DSC and proton conductivity. Proton conductivity of the SPEEK membranes was compared with one of the Nafion^® membranes with relative humidity. The porosity of the catalyst electrodes was calculated using the properties of catalyst, ionomer solution and solvent. As a result, the performance of the new type polymer (i.e., SPEEK in this study)-based MEA with the similar membrane conductivity and porosity of the catalyst electrode in the Nafion^® MEA was similar to that of the Nafion^® MEA.     

Nafion/poly(1-vinyl-1,2,4-triazole) blends as proton conducting membranes for polymer electrolyte membrane fuel cells

In this study, proton conducting Nafion-poly(1-vinyl-1,2,4-triazole) blends are produced. Nafion/polymer blend membranes are prepared by means of film casting from the Nafion-PVTri solutions at several molar ratios of PVTri repeat unit to -SO₃H. The chemical structure of the homopolymer PVTri is confirmed by FT-IR and ¹³C NMR. Thermal properties are investigated via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) and the results illustrated that all these Nafion-PVTri electrolytes are thermally stable at least up to 300 °C. The membrane properties are further characterized for their morphology by scanning electron microscopy (SEM) and water uptake measurements. The methanol permeability of these membranes is measured and the results exhibited that they have quite lower methanol permeability compared to pristine Nafion112. The electrochemical properties of PVTri are investigated by cyclic voltammetry. The conductivity of Nafion-P(VTri)₁ blend membranes is measured to be 5.3 × 10⁻⁴ S cm⁻¹ at 220 °C, in anhydrous state. The conductivity of blend increased at least three orders of magnitude up on hydration, i.e., exceeding 10⁻³ S cm⁻¹ with RH = 50% at ambient temperature.     

Chelating agent assisted heat treatment of carbon supported cobalt oxide nanoparticle for use as cathode catalyst of polymer electrolyte membrane fuel cell (PEMFC)

Cobalt-based catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cell (PEMFC) have been successfully incorporated cobalt oxide (Co₃O₄) onto Vulcan XC-72 carbon powder by thermal decomposition of Co-ethylenediamine complex (ethylenediamine, NH₂CH₂CH₂NH₂, denoted en) at 850 °C. The catalysts were prepared by adsorbing the cobalt complexes [Co(en)(H₂O)₄]³⁺, [Co(en)₂(H₂O)₂]³⁺ and [Co(en)₃]³⁺ on commercial XC-72 carbon black supports, loading amount of Co with respect to carbon black was about 2%, the resulting materials have been pyrolyzed under nitrogen atmosphere to create CoO_x/C catalysts, donated as E1, E2, and E3, respectively. The composite materials were characterized using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). Chemical compositions of prepared catalysts were determined using inductively-coupled plasma-atomic emission spectroscopy (ICP-AES). The catalytic activities for ORR have been analyzed by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). The electrocatalytic activity for oxygen reduction of E2 is superior to that of E1 and E3. Membrane electrode assemblies (MEAs) containing the synthesized CoO_x/C cathode catalysts were fabricated and evaluated by single cell tests. The E2 cathode performed better than that of E1 and E3 cathode. This can be attributed to the enhanced activity for ORR, in agreement with the composition of the catalyst that CoO co-existed with Co₃O₄. The maximum power density 73 mW cm⁻² was obtained at 0.3 V with a current density of 240 mA cm⁻² for E2 and the normalized power density of E2 is larger than that that of commercial 20 wt.% Pt/C-ETEK.     

Efficient fault diagnosis method of PEMFC thermal management system for various current densities

The temperature of a fuel cell has a considerable impact on the saturation of a membrane, electrochemical reaction speed, and durability. So thermal management is considered one of the critical issues in polymer electrolyte membrane fuel cells. Therefore, the reliability of the thermal management system is also crucial for the performance and durability of a fuel cell system. In this work, a methodology for component-level fault diagnosis of polymer electrolyte membrane fuel cell thermal management system for various current densities is proposed. Specifically, this study suggests fault diagnosis using limited data, based on an experimental approach. Normal and five component-level fault states are diagnosed with a support vector machine model using temperature, pressure, and fan control signal data. The effects of training data at different operating current densities on fault diagnosis are analyzed. The effects of data preprocessing method are investigated, and the cause of misdiagnosis is analyzed. On this basis, diagnosis results show that the proposed methodology can realize efficient component-level fault diagnosis using limited data. The diagnosis accuracy is over 92% when the residual basis scaling method is used, and data at the highest operating current density is used to train the support vector machine.     

Performance and stability characteristics of MEAs with carbon-supported Pt and Pt1Ni1 nanoparticles as cathode catalysts in PEM fuel cell

Polarization curves of membrane electrode assemblies (MEAs) containing carbon-supported platinum (Pt/C) and platinum-nickel alloy (Pt₁Ni₁/C) as cathode catalysts were obtained for durability test as a function of time over 1100 h at constant current. Charge transfer resistance was measured using electrochemical impedance spectroscopy and postmortem analysis such as X-ray diffraction and high-resolution transmission electron microscopy was conducted in order to elucidate the degradation factors of each MEA. Our results demonstrate that the reduced performance of MEAs containing Pt₁Ni₁/C as a cathode catalyst was due to decreased oxygen reduction reaction caused by the corrosion of Ni, whereas that of MEAs containing Pt/C was because of reduced electrochemical surface area induced by increased Pt particle size.